EP0538673B1 - Masses à couler de polyuréthane substantiellement compacts, clairs et stérilisables à la vapeur chaude, non zytotoxique, procédé pour leur préparation et leur utilisation, en particulier pour des articles techniques médicinaux - Google Patents
Masses à couler de polyuréthane substantiellement compacts, clairs et stérilisables à la vapeur chaude, non zytotoxique, procédé pour leur préparation et leur utilisation, en particulier pour des articles techniques médicinaux Download PDFInfo
- Publication number
- EP0538673B1 EP0538673B1 EP92117083A EP92117083A EP0538673B1 EP 0538673 B1 EP0538673 B1 EP 0538673B1 EP 92117083 A EP92117083 A EP 92117083A EP 92117083 A EP92117083 A EP 92117083A EP 0538673 B1 EP0538673 B1 EP 0538673B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- ppm
- bis
- polyol
- cytotoxic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 76
- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title claims description 6
- 238000005266 casting Methods 0.000 title description 45
- 238000002360 preparation method Methods 0.000 title description 2
- 229920005862 polyol Polymers 0.000 claims abstract description 109
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000004359 castor oil Substances 0.000 claims abstract description 22
- 235000019438 castor oil Nutrition 0.000 claims abstract description 21
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 21
- 231100000065 noncytotoxic Toxicity 0.000 claims abstract description 21
- 230000002020 noncytotoxic effect Effects 0.000 claims abstract description 21
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract 12
- 239000003814 drug Substances 0.000 claims abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 82
- -1 polyoxypropylene- Polymers 0.000 claims description 52
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 43
- 229920001451 polypropylene glycol Polymers 0.000 claims description 39
- 229910001414 potassium ion Inorganic materials 0.000 claims description 33
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 30
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 20
- 229930006000 Sucrose Natural products 0.000 claims description 20
- 239000005720 sucrose Substances 0.000 claims description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 12
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 12
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000600 sorbitol Substances 0.000 claims description 12
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 11
- CTNQWKMCGAICKY-UHFFFAOYSA-K 4-ethyl-2-sulfanyloctanoate;octyltin(3+) Chemical compound CCCCCCCC[Sn+3].CCCCC(CC)CC(S)C([O-])=O.CCCCC(CC)CC(S)C([O-])=O.CCCCC(CC)CC(S)C([O-])=O CTNQWKMCGAICKY-UHFFFAOYSA-K 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- VXGIVDFKZKMKQO-UHFFFAOYSA-L dioctyltin isooctylthioglycolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCCCCCC)(CCCCCCCC)SCC(=O)OCC(CC)CCCC VXGIVDFKZKMKQO-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000003462 bioceramic Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 description 76
- 239000004721 Polyphenylene oxide Substances 0.000 description 31
- 229920000570 polyether Polymers 0.000 description 31
- 235000011187 glycerol Nutrition 0.000 description 28
- 239000003513 alkali Substances 0.000 description 25
- 239000011541 reaction mixture Substances 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 17
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 238000004382 potting Methods 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012510 hollow fiber Substances 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 6
- BPRJQFIHEGORJE-UHFFFAOYSA-N 2-(1-hydroxypropan-2-yloxy)propan-1-ol 1-(2-hydroxypropoxy)propan-2-ol Chemical compound CC(O)COCC(C)O.CC(CO)OC(C)CO BPRJQFIHEGORJE-UHFFFAOYSA-N 0.000 description 5
- 239000004808 2-ethylhexylester Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 231100000433 cytotoxic Toxicity 0.000 description 5
- 230000001472 cytotoxic effect Effects 0.000 description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- SMNOVRZDAZZQTI-UHFFFAOYSA-N 1-[dibutyl(dodecanoyl)stannyl]dodecan-1-one Chemical compound CCCCCCCCCCCC(=O)[Sn](CCCC)(CCCC)C(=O)CCCCCCCCCCC SMNOVRZDAZZQTI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000005548 dental material Substances 0.000 description 2
- RFAIKXASDCRKEP-UHFFFAOYSA-N dioctyl(sulfanylidene)tin Chemical compound CCCCCCCC[Sn](=S)CCCCCCCC RFAIKXASDCRKEP-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- CDLODZZZJYQTAO-UHFFFAOYSA-K 4-ethyl-2-hydroxyoctanethioate octyltin(3+) Chemical compound C(C)C(CC(C(=S)[O-])O)CCCC.C(C)C(CC(C(=S)[O-])O)CCCC.C(C)C(CC(C(=S)[O-])O)CCCC.C(CCCCCCC)[Sn+3] CDLODZZZJYQTAO-UHFFFAOYSA-K 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000012925 biological evaluation Methods 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- HZHREVFVFOBHSK-UHFFFAOYSA-L dioctyltin(2+);4-ethyl-2-sulfanyloctanoate Chemical compound CCCCC(CC)CC(S)C([O-])=O.CCCCC(CC)CC(S)C([O-])=O.CCCCCCCC[Sn+2]CCCCCCCC HZHREVFVFOBHSK-UHFFFAOYSA-L 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical class [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- BDIWFCKBPZPBQT-UHFFFAOYSA-N tributyl(tributylstannylsulfanyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)S[Sn](CCCC)(CCCC)CCCC BDIWFCKBPZPBQT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
- B01D63/023—Encapsulating materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
Definitions
- catalyst-free casting compounds are made Castor oil 4,4'-MDI, toluylene diisocyanate or phenylene diisocyanate prepolymers with terminal NCO groups and a crosslinking agent, that contains castor oil and / or an ester an at least tetravalent alcohol and a hydroxy or Aliphatic carboxylic acid having epoxy groups with at least 12 carbon atoms.
- catalyst-free Potting compounds made from a prepolymer from castor oil and polyoxypropylene glycol and 4,4'-MDI, and a crosslinking agent based on an ester of one polyhydric alcohol with 2 or 3 hydroxyl groups and one aliphatic Carboxylic acid with at least 12 carbon atoms and one or several hydroxyl and / or epoxy groups.
- suitable polyisocyanates for the preparation of the prepolymers are also mentioned: 2,4- and 2,6-tolylene diisocyanate or phenylene diisocyanate.
- Crosslinking agents also come from monoesters and / or diesters Ethylene glycol and ricinoleic acid, trimethylolpropane or ethane in Consideration.
- physiologically harmless PU molding materials in particular for embedding hollow fibers in dialyzers, are produced by reacting highly reactive, low-viscosity and storage-stable mixed prepolymers consisting of solid, highly reactive aromatic diisocyanates and less reactive, liquid diisocyanates in a weight ratio of 1: 5 to 5: 1 and polyols, with polyols from the castor oil group and / or its transesterification products, high-purity polyester and polyoxytetramethylene glycol.
- PU potting compounds composed of a PU prepolymer having isocyanate end groups and an N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine-containing polyol mixture are the subject of US Pat. No. 4,224,164.
- US-A- 4,742,112 are used to produce PU casting compounds for electrical equipment as a polyol component, mixtures of 10 to 60% by weight of a ricinoleic acid ester and 90 to 40% by weight of a C 2 to C 6 hydrocarbon polymer with at least one hydroxyl group.
- two-component PU formulations which are not cytotoxic in the hardened state and are suitable as casting compounds for separating devices consist of at least one NCO-terminated prepolymer, at least one Polyol and a catalytically effective amount of a dicarboxylated dialkyltin compound.
- PU casting compounds catalyzed with tin-sulfur compounds for embedding hollow cellulose fibers in dialyzers are described in DD-A-155 777.
- the aforementioned PU casting compounds can be used in medical-technical Devices or molded parts for this processed and before their Use with ethylene oxide and / or sterilized with ⁇ -rays will.
- this type of sterilization has the disadvantage that that remaining traces of ethylene oxide in some patients have allergies can trigger and the ⁇ -rays unidentifiable Fission products can form, so that the patient has a certain Health risk caused by dialysis is not complete can be excluded.
- the state of the art known casting compounds are also not sufficiently temperature and chemical resistant so that it does not require hot steam sterilization at a temperature of 121 ° C for a period of Can be subjected to 20 minutes.
- PU casting compounds cannot be processed with every type of fiber.
- cellulose fibers from PU casting compounds are used Castor oil base attacked and damaged.
- the casting compounds produced can be used directly after potting and within a period of approximately Cut 30 minutes later; however, they harden very quickly after, so that the moldings, preferably dialysis filters already can no longer be cut after 24 hours. This adverse behavior leads especially to production disruptions and product losses at the end of work.
- Find to manufacture the PU casting compounds use PU formulations as structural components primary, secondary and / or tertiary amino groups and contain reactive hydrogen atoms bound, so are the obtained ones Potting compounds unstable against sterilization with peracetic acid.
- EP-A-0 393 545 and EP-A-0 413 265 transparent, steam-sterilizable, essentially compact PU potting compounds described using of diphenylmethane diisocyanates modified with selected compounds (MDI).
- modified MDI liquid at 23 ° C are produced by reacting an MDI isomer mixture, which, based per 100 parts by weight, consists of 60 to 90 parts by weight of 4,4'-MDI, 40 up to 8 parts by weight of 2,4'-MDI and 0 to 5 parts by weight of 2,2'-MDI, with a polyoxypropylene polyol started with glycerin and / or trimethylpolypropane with a molecular weight of 350 to 800.
- EP-A-0 413 265 describes the use of modified MDI's obtained by reaction of 4,4'-MDI or 2,4'-MDI or MDI isomer mixtures with selected special, at least tetrafunctional polyoxypropylene polyols and / or Polyoxypropylene-polyoxyethylene-polyols containing polymerized Ethylene oxide units of up to 80% by weight for production the PU casting compounds.
- PU casting compounds have an increased temperature resistance and improved hydrolysis resistance.
- Advantageous is also that the maximum curing temperature by the released heat of reaction of the polyaddition reaction reached can be significantly reduced.
- liability problems arise after repeated sterilizations between PU casting compounds and other materials, such as. B.
- the PU casting compounds may occur.
- the PU casting compounds detach from the housing part of a dialyzer.
- Such Symptoms of detachment occurred particularly when through Disturbances during steam sterilization the temperature of 121 ° C and / or the sterilization time has exceeded 20 minutes has been.
- the object of the present invention was the known PU casting compounds, preferably those in EP-A-0 393 545 and EP-A-0 413 265 described to improve by appropriate measures. Liability in particular should be improved between the pu casting compounds and other materials, so that at least brief disruptions during sterilization no detachment of the PU casting compounds.
- the invention further relates to a method for production the transparent, steam-sterilizable, non-cytotoxic, essentially compact PU casting compounds according to claim 18 and the use of the PU casting compounds for embedding of hollow fibers preferably made of polysulfones or polycarbonates in dialysis machines, for the production of medical-technical Articles and for binding bioceramic coatings Endoprostheses according to claim 17.
- the PU casting compounds according to the invention are transparent, not cytotoxic and not only have improved adhesion other materials, e.g. B. polycarbonates, at elevated temperatures over a longer period, but the reaction mixtures can also be poured without foaming.
- the PU casting compounds can be cut after 2 hours, harden however not so strongly after, so that they also after more than Are still capable of being cut for 24 hours.
- the PU casting compounds according to the invention with all the usual types of hollow fibers, such as B. cuprophane, polysulfone, polycarbonate or Cellulose fibers can be processed and the polycarbonates before No pre-treatment by corona discharge to improve need the adhesive strength.
- the PU casting compounds are against percarboxylic acids stable, so that moldings made of such potting compounds can be sterilized with peracetic acid.
- This will be essentially complete degassing starting components at temperatures of expedient 18 to 70 ° C, preferably from 22 to 60 ° C mixed intensively.
- reaction mixtures that have a total Alkali ions, preferably potassium ions, of preferably 8 to 110 ppm, in particular 15 to 50 ppm, are suitable Forming tool introduced and over a period of 0.3 harden to 4 hours, preferably 1 to 3 hours calmly.
- the transparent, steam-sterilisable, non-cytotoxic, essentially compact, PU casting compounds in particular use for embedding hollow fibers, such as. of cuprophane and preferably of polysulfone, Polycarbonate fibers or hollow cellulose fibers in dialyzers, the dialysis machines, in particular the sleeve for the dialysis filter, expediently from a polycarbonate based on Bisphenol A.
- the PU casting compounds according to the invention are also suitable for production of medical-technical articles and for binding Bioceramic coatings on endoprostheses.
- the PU casting compounds are not cytotoxic, transparent, show no interaction with the hollow fibers, have a strong Adhesion to polycarbonate and are embedded without destroying the Hollow fibers easy to cut.
- the resulting MDI mixture modified with urethane groups had an NCO content of 20.5% by weight and a viscosity 25 ° C from 2100 m.Pa.s.
- the reaction mixture had a potassium ion content of 25.4 ppm and showed a gel time of 350 seconds.
- the molded body had a hardness of 96.5 Shore-A after 24 hours Storage at 23 ° C.
- the molded article produced by the centrifugal process was immediate after demoulding, bubble-free and dry and after Can be cut for 2 hours.
- Dialysers manufactured could at least at 121 ° C 6 times steam sterilized, without damaging the Molded body appeared.
- the cytotoxic safety check published according to the guidelines "Guide line ISO / TR 7405-1984 (E)" from the International Organization for Standardization: "Biological Evaluation of Dental Materials and the Pre-Standard DIN V 13930, Sept. 1990 "” Biological tests of dental materials " was passed.
- the molded article was stored for 10 days at 23 ° C. in 7 wt .-% aqueous peracetic acid no decrease in the peracetic acid content.
- the obtained MDI mixture modified with urethane groups had an NCO content of 20.3 wt .-% and a viscosity at 25 ° C of 3324 m.
- the reaction mixture had a potassium ion content of 39 ppm and showed a gel time of 203 seconds.
- the obtained MDI mixture modified with urethane groups had an NCO content of 20.2 wt .-% and a viscosity at 25 ° C of 3266 m.
- the reaction mixture had a potassium content of 37.4 ppm and showed a gel time of 124 seconds.
- the molded body had one Hardness of 96 Shore-A after storage for 24 hours at 23 ° C.
- the adhesion of the PU gypsum mass to the polystyrene was so strong that the components could not be separated again.
- a 10 days storage of the shaped body at 23 ° C in 7 wt .-% aqueous Peracetic acid showed no drop in peracetic acid content.
- B component MDI mixture modified with urethane groups an NCO content of 20.23% by weight analogous to the information in Example 4.
- the reaction mixture had a potassium ion content of 53.5 ppm and showed a gel time of 177 seconds.
- the molded body had a hardness of 96 Shore-A after 24 hours Storage at 23 ° C.
- the adhesion between polystyrene and the PU potting compound was excellent.
- B component MDI mixture modified with urethane groups according to Example 6.
- the reaction mixture had a potassium ion content of 37.4 ppm and showed a gel time of 234 seconds.
- the shaped body After 24 hours of storage at 23 ° C., the shaped body had a hardness of 96 Shore-A. The liability between the PU potting compound and the polystyrene was excellent.
- B component MDI mixture modified with urethane groups according to Example 6.
- the reaction mixture had a potassium ion content of 37.4 ppm and showed a gel time of 520 seconds.
- the shaped body After 24 hours of storage at 23 ° C., the shaped body had a hardness of 91 Shore-A. The liability between the PU potting compound and the polystyrene was satisfactory.
- the resulting MDI mixture modified with urethane groups had an NCO content of 20.15% by weight and a viscosity 25 ° C from 2414 m.Pa.s.
- the reaction mixture had a potassium ion content of 69.4 ppm and showed a gel time of 173 seconds.
- the shaped body After 24 hours of storage at 23 ° C., the shaped body had a hardness of 75 Shore-A. The liability between the PU potting compound and the polystyrene was satisfactory.
- a component analogous to Example 5, but with a content of Catalyst combination of 0.02 parts by weight.
- the molded article produced by the centrifugal process was immediate after demoulding, bubble-free and dry and after Can be cut for 2 hours.
- Dialysers manufactured could at least at 121 ° C 6 times steam sterilized, without damaging the Molded body appeared. Furthermore, a 10 day storage of the Shaped body at 23 ° C in 7 wt .-% aqueous peracetic acid no drop in peracetic acid content. The cytotoxic safety check according to the guidelines line ISO / TR 7405-1984 (E) was passed.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- External Artificial Organs (AREA)
Claims (17)
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes, préparées par la réactiona) de diisocyanates de diphénylméthane modifiés, d'une viscosité à 23°C de 100 à 8000 mPas avecb) des composés comprenant au moins deux atomes d'hydrogène réactifs,
en présence ou en l'absencec) de catalyseurs,b1) 1 à 20% en poids d'au moins un polyétherpolyol d'une fonctionnalité moyenne de 3 à 8, d'un indice d'hydroxyle de 200 à 1000 et d'une teneur en ions de métaux alcalins de 150 à 1200 ppm, etb2) 99 à 80% en poids d'huile de ricin et/ou d'au moins un polyétherpolyol d'une fonctionnalité de 2 à 3, d'un indice d'hydroxyle de 90 à 200 et d'une teneur en ions de métaux alcalins inférieure à 10 ppm. - Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le composant de mélange (b2) se compose d'huile de ricin.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le composant de mélange (b) est constitué d'un polyétherpolyol trifonctionnel d'un indice d'hydroxyle de 120 à 180 et d'une teneur en ions de métaux alcalins inférieure à 5 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que les ions de métaux alcalins dans (b1) se composent d'ions potassium.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le polyétherpolyol (b) est un polyoxyéthylènepolyol amorcé au triméthylolpropane, d'un indice d'hydroxyle se situant dans la plage de 632 à 970 et d'une teneur en ions potassium qui varie de 400 à 600 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le polyétherpolyol (b1) est un polyoxypropylènepolyol amorcé à la glycérine et/ou au triméthylolpropane, d'un indice d'hydroxyle qui varie dans la plage de 210 à 480 et d'une teneur en ions potassium qui fluctue dans la plage de 400 à 600 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le polyétherpolyol (b1) se compose d'au moins un polyoxypropylènepolyol d'une fonctionnalité moyenne de 4 à 8 et d'un indice d'hydroxyle de 230 à 500, obtenu en recourant à l'emploi de saccharose ou de sorbite, ou de mélanges de saccharose et de sorbite, à titre de molécules amorceuses, où à titre de coamorceur, on utilise complémentairement et conjointement de l'eau, du propylèneglycol, de la glycérine ou des mélanges d'au moins deux des coamorceurs susmentionnés, avec la condition que les polyétherpolyols possèdent une teneur en ions de métaux alcalins qui fluctue de 400 à 700 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le polyétherpolyol (b1) est un polyoxypropylène- ou polyoxyéthylènepolyol ou un mélange de ces polyoxyalkylènepolyols, d'un indice d'hydroxyle de 450 à 750, que l'on obtient par l'utilisation de la pentaérythrite, ou d'un mélange de pentaérythrite et de glycérine et/ou de triméthylolpropane à titre de molécules amorceuses, avec la condition que les polyétherpolyols possèdent une teneur en ions de métaux alcalins qui varie de 150 à 800 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que, à titre de diisocyanates de diphénylméthane modifiés (a), on utilise des prépolymères de NCO contenant en liaison des radicaux uréthanne, d'une teneur en NCO de 24 à 15% en poids, que l'on prépare par la réaction de, par rapport au poids total, au moins 85% en poids d'un prépolymère contenant des radicaux NCO, d'une teneur en NCO de 29 à 21% en poids, que l'on obtient, d'une part, par la réaction du diisocyanate de 4,4'-diphénylméthane avec le dipropylèneglycol ou au moins un polyoxypropylèneglycol, d'un indice d'hydroxyle allant jusqu'à 400, ou d'un mélange de dipropylèneglycol et d'au moins un polyoxypropylèneglycol, d'un indice d'hydroxyle allant jusqu'à 400 et d'au maximum 15% en poids d'huile de ricin.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que, à titre de diisocyanates de diphénylméthane modifiés (a), on utilise des prépolymères de NCO contenant en liaison des radicaux uréthanne, d'une teneur en NCO de 24 à 15% en poids, qui sont préparés par la réaction de, par rapport au poids total, au moins 85% en poids d'un prépolymère contenant des radicaux NCO, d'une teneur en NCO de 29 à 21% en poids, que l'on obtient, d'une part, par la réaction du diisocyanate de 4,4'-diphénylméthane avec le dipropylèneglycol ou au moins un polyoxypropylèneglycol, d'un indice d'hydroxyle de 50 à 250, ou d'un mélange de dipropylèneglycol et d'au moins un polyoxypropylèneglycol, d'un indice d'hydroxyle de 50 à 250, et d'au maximum 15% en poids d'un polyoxyalkylèneglycol amorcé à la glycérine, au triméthylolpropane, ou à l'aide d'un mélange de glycérine et de triméthylolpropane, d'un indice d'hydroxyle de 90 à 200 et d'une teneur en ions de métaux alcalins inférieure à 10 ppm, appartenant au groupe des polyoxypropylène-, polyoxypropylène-polyoxyéthylène- et polyoxyéthylène-polyoxypropylène-polyols.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que les composants constitutifs (a) et (b) possèdent une teneur totale en ions de métaux alcalins de 8 à 110 ppm.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que le catalyseur (c) se compose de (2-éthylhexylthioglycolate) de mono-n-octylétain, de bis-(2-éthylhexylthioglycolate) de di-n-octylétain ou de dilaurate de dibutylétain.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que l'on utilise, à titre de catalyseur (c), une combinaison catalytique qui se compose, par rapport au poids total, de 1 à 99% en poids de (2-éthylhexylthioglycolate) de mono-n-octylétain et de 99 à 1% en poids de bis-(2-éthylhexylthioglycolate) de di-n-octylétain.
- Masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1, caractérisées en ce que l'on utilise, à titre de catalyseur (c), une combinaison catalytique qui se compose, par rapport au poids total, de 94% en poids de bis-(2-éthylhexylthioglycolate) de di-n-octylétain et 6% en poids de tris-(2-éthylhexylthioglycolate) de mono-n-octylétain.
- Procédé de préparation de masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes par la réactiona) de diisocyanates de diphénylméthane modifiés, d'une viscosité à 23°C de 100 à 800 mPas, avecb) des composés comportant au moins deux atomes d'hydrogène réactifs,
en présence ou en l'absence dec) des catalyseurs,b1) 1 à 20% en poids d'au moins un polyétherpolyol d'une fonctionnalité moyenne de 3 à 8, d'un indice d'hydroxyle de 200 à 1000 et d'une teneur en ions de métaux alcalins de 150 à 1200 ppm, etb2) 99 à 80% en poids d'huile de ricin et/ou d'au moins un polyétherpolyol d'une fonctionnalité de 2 à 3, d'un indice d'hydroxyle de 90 à 200 et d'une teneur en ions de métaux alcalins inférieure à 10 ppm. - Procédé suivant la revendication 15, caractérisé en ce que l'on utilise les composants constitutifs (a) et (b) en proportions telles que l'indice d'isocyanates possède une valeur qui varie de 100 à 130.
- Utilisation des masses de remplissage ou de scellement en polyuréthanne transparentes, stérilisables à la vapeur chaude, non cytotoxiques, essentiellement compactes suivant la revendication 1 pour l'incorporation de fibres creuses en polysulfones ou en polycarbonates dans les appareils de dialyse, pour la fabrication d'articles médico-techniques, ainsi que pour la liaison de revêtements biocéramiques à des endoprothèses.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4134693 | 1991-10-21 | ||
DE4134693A DE4134693A1 (de) | 1991-10-21 | 1991-10-21 | Transparente, heissdampfsterilisierbare, nicht zytotoxische, im wesentlichen kompakte polyurethan-vergussmassen, verfahren zu ihrer herstellung und ihre verwendung, insbesondere fuer medizinisch-technische artikel |
CA002082019A CA2082019C (fr) | 1991-10-21 | 1992-11-03 | Compositions d'enrobage en polyurethane transparentes, autoclavables, non cytotoxiques et essentiellement compactes, mode de preparation et applications particulieres au domaine de l'instrumentation medicale |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0538673A2 EP0538673A2 (fr) | 1993-04-28 |
EP0538673A3 EP0538673A3 (en) | 1993-06-02 |
EP0538673B1 true EP0538673B1 (fr) | 1998-01-07 |
Family
ID=25675635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92117083A Expired - Lifetime EP0538673B1 (fr) | 1991-10-21 | 1992-10-07 | Masses à couler de polyuréthane substantiellement compacts, clairs et stérilisables à la vapeur chaude, non zytotoxique, procédé pour leur préparation et leur utilisation, en particulier pour des articles techniques médicinaux |
Country Status (9)
Country | Link |
---|---|
US (1) | US5306798A (fr) |
EP (1) | EP0538673B1 (fr) |
JP (1) | JP3344740B2 (fr) |
KR (1) | KR100234858B1 (fr) |
AT (1) | ATE161859T1 (fr) |
CA (1) | CA2082019C (fr) |
DE (2) | DE4134693A1 (fr) |
DK (1) | DK0538673T3 (fr) |
ES (1) | ES2110460T3 (fr) |
Families Citing this family (38)
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US5849504A (en) * | 1989-08-11 | 1998-12-15 | Amoco Corporation | Nucleic acid probes and methods for detecting Pneumocystis carinii |
US5328954A (en) * | 1993-04-16 | 1994-07-12 | Icet, Inc. | Encrusting and bacterial resistant coatings for medical applications |
JPH06296834A (ja) * | 1993-04-20 | 1994-10-25 | Kanegafuchi Chem Ind Co Ltd | 中空糸型フィルター |
DE4315874A1 (de) * | 1993-05-12 | 1994-11-17 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Schaumstoffen |
DE19506671C2 (de) * | 1995-02-25 | 1999-11-18 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Schaumstoffen |
US5646195A (en) * | 1995-03-07 | 1997-07-08 | The Dow Chemical Company | Catalyst for polyurethane carpet backings and carpets prepared therewith |
US5596059A (en) * | 1995-07-26 | 1997-01-21 | Arco Chemical Technology, L.P. | Polyether polyols suitable for mflexible polyurethane foam prepared by co-initiation of aqueous solutions of solid polyhydroxyl initiators |
CA2188503A1 (fr) * | 1995-12-22 | 1997-06-23 | Neil H. Nodelman | Systemes de moulage par transfert de resine polyurethanne |
FR2766828B1 (fr) * | 1997-07-31 | 1999-10-22 | Hospal Ind | Compositions generatrices de polyurethane non cytotoxique |
FR2766829B1 (fr) * | 1997-07-31 | 1999-10-22 | Hospal Ind | Compositions generatrices de polyurethane non cytotoxique |
DE19811289A1 (de) * | 1998-03-16 | 1999-09-23 | Basf Ag | Kompakte, transparente Polyisocyanat-Polyadditionsprodukte |
DE19947190A1 (de) * | 1999-10-01 | 2001-04-05 | Basf Ag | Transparente, heissdampfsterilisierbare, nicht zytotoxische Polyurethan-Vergussmassen, Verfahren zu ihrer Herstellung und ihre Verwendung, insbesondere für medizinisch-technische Artikel |
DE19947191A1 (de) * | 1999-10-01 | 2001-04-05 | Basf Ag | Transparente, heissdampfsterilisierbare, nicht zytotoxische Polyurethan-Vergussmassen, Verfahren zu ihrer Herstellung und ihre Verwendung, insbesondere für medizinisch-technische Artikel |
DE19947192A1 (de) * | 1999-10-01 | 2001-04-05 | Basf Ag | Transparente, heissdampfsterilisierbare, nicht zytotoxische Polyurethan-Vergussmassen, Verfahren zu ihrer Herstellung und ihre Verwendung, insbesondere für medizinisch-technische Artikel |
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DE502007003677D1 (de) | 2006-10-04 | 2010-06-17 | Basf Se | Vergussmassen auf basis von polyurethan |
JP5375606B2 (ja) * | 2007-06-21 | 2013-12-25 | 株式会社カネカ | 耐久性に優れた湿潤時潤滑性表面コーティング用組成物、コーティング液、表面コーティング、ならびに表面コーティング方法と、この表面コーティングを有する医療用具 |
CN103417332B (zh) | 2008-05-30 | 2015-10-07 | 凯希特许有限公司 | 超吸收性减压伤口敷料和系统 |
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JP5797475B2 (ja) * | 2011-06-23 | 2015-10-21 | 第一工業製薬株式会社 | ポリウレタン樹脂組成物およびそれを用いてなる中空糸膜モジュール |
US9832902B2 (en) * | 2013-05-31 | 2017-11-28 | Elantas Pdg, Inc. | Formulated resin compositions for flood coating electronic circuit assemblies |
EP2997099B1 (fr) * | 2013-05-31 | 2020-10-14 | ELANTAS PDG Inc. | Compositions des résins polyuréthane pour le revêtement de surface des élements contenant un circuit électronique |
CN106471087B (zh) | 2014-03-12 | 2020-07-07 | 艾伦塔斯Pdg有限公司 | 用于反渗透组件的聚氨酯粘合剂 |
US9556305B2 (en) | 2014-04-14 | 2017-01-31 | Crosslink Technology Inc. | Non-cytotoxic urethane elastomer |
JP2017536459A (ja) | 2014-11-26 | 2017-12-07 | サイテク・インダストリーズ・インコーポレーテツド | 多液型ポリウレタン組成物、その物品、及び製造方法 |
WO2016138246A1 (fr) * | 2015-02-26 | 2016-09-01 | Sabic Global Technologies B.V. | Mélanges de polymères comprenant du polycarbonate et du méthacrylate de polyméthyle |
EP3280516B1 (fr) | 2015-04-09 | 2019-12-18 | Elantas Pdg, Inc. | Adhésifs en polyuréthane pour modules d'osmose inverse |
JP7155156B2 (ja) | 2017-05-05 | 2022-10-18 | ビーエーエスエフ ソシエタス・ヨーロピア | フィルター要素の製造における中空繊維を埋め込むための貯蔵安定性ポリウレタン注入用化合物 |
EP3619248B1 (fr) | 2017-05-05 | 2023-01-11 | Basf Se | Mélange de scellement polyuréthane stable au stockage destiné à enrober des fibres creuses lors de la fabrication d'éléments de filtre |
WO2021083851A1 (fr) | 2019-10-30 | 2021-05-06 | Basf Se | Composé de coulée de polyuréthane à réactivité améliorée pour l'incorporation de fibres creuses dans la production d'éléments filtrants |
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US4202957A (en) * | 1974-09-09 | 1980-05-13 | The Upjohn Company | Thermoplastic polyurethane elastomers from polyoxypropylene polyoxyethylene block copolymers |
IT1115397B (it) * | 1976-11-05 | 1986-02-03 | Nl Industries Inc | Composizione poliuretanica e relativi articoli |
US4256617A (en) * | 1979-11-01 | 1981-03-17 | Nl Industries, Inc. | Catalyzed non-toxic polyurethane forming compositions and separatory devices employing the same |
DE3029204A1 (de) * | 1980-08-01 | 1982-04-01 | Basf Ag, 6700 Ludwigshafen | Polyether-polyol-mischungen und deren verwendung |
US4742112A (en) * | 1987-01-23 | 1988-05-03 | Caschem, Inc. | Ricinoleate modified hydrocarbon polyols |
DE3912531C2 (de) * | 1989-04-17 | 1998-08-27 | Basf Ag | Glasklare, heißdampfsterilisierbare, kompakte Polyurethan-Vergußmassen, Verfahren zu ihrer Herstellung und ihre Verwendung, insbesondere für medizinisch technische Artikel |
DE3927244A1 (de) * | 1989-08-18 | 1991-02-21 | Basf Ag | Transparente, heissdampfsterilisierbare, kompakte polyurethan-vergussmassen, verfahren zu ihrer herstellung und ihre verwendung, insbesondere fuer medizinisch technische artikel |
-
1991
- 1991-10-21 DE DE4134693A patent/DE4134693A1/de not_active Withdrawn
-
1992
- 1992-10-07 AT AT92117083T patent/ATE161859T1/de not_active IP Right Cessation
- 1992-10-07 EP EP92117083A patent/EP0538673B1/fr not_active Expired - Lifetime
- 1992-10-07 DE DE59209107T patent/DE59209107D1/de not_active Expired - Lifetime
- 1992-10-07 DK DK92117083.3T patent/DK0538673T3/da active
- 1992-10-07 ES ES92117083T patent/ES2110460T3/es not_active Expired - Lifetime
- 1992-10-16 JP JP27846392A patent/JP3344740B2/ja not_active Expired - Lifetime
- 1992-10-21 KR KR1019920019302A patent/KR100234858B1/ko not_active IP Right Cessation
- 1992-11-02 US US07/970,749 patent/US5306798A/en not_active Expired - Fee Related
- 1992-11-03 CA CA002082019A patent/CA2082019C/fr not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3016404A (en) * | 1959-09-28 | 1962-01-09 | Allied Chem | Purification of crude alkylene oxide polyether |
Also Published As
Publication number | Publication date |
---|---|
KR930007999A (ko) | 1993-05-20 |
DE4134693A1 (de) | 1993-04-22 |
KR100234858B1 (ko) | 1999-12-15 |
DE59209107D1 (de) | 1998-02-12 |
ES2110460T3 (es) | 1998-02-16 |
CA2082019A1 (fr) | 1994-05-04 |
JPH05239176A (ja) | 1993-09-17 |
ATE161859T1 (de) | 1998-01-15 |
DK0538673T3 (da) | 1998-02-09 |
EP0538673A2 (fr) | 1993-04-28 |
JP3344740B2 (ja) | 2002-11-18 |
US5306798A (en) | 1994-04-26 |
EP0538673A3 (en) | 1993-06-02 |
CA2082019C (fr) | 1997-06-03 |
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